Structural changes are detected at the interface between polycrystalline Ag electrodes and electrolyte solutions containing surfactants as probe molecules. Capacitance and impedance measurements indicate that in aqueous solutions water and 1-butanol molecules change their position on the electrode due to dipole-field interaction. In methanolic solutions such a change is indicated to occur only for triphenyphosphine oxide molecules. The above changes in both solvents are taking place along with the transition of the adsorbed layer from a dense liquid state to a thinner one with increasing negative potentials. (C) 2014 Elsevier B.V. All rights reserved.